Photographic materials for the silver dyestuff bleaching process



United States Patent ice 3,443,953

Patented May 13, 1969 3 443 953 are advantageously used, in which R represents a ben- PHOTOGRAPHIC M i i ALS FOR THE SILVER zene or a naphthalene residue containing at least two DYEST FF BLEA HIN P OCESS sulphonic acid groups, R represents a benzene or a naph- Hansrolf Loeif Bern, swit zerlafii, ziisignor to Ciba thalene resldue bound IA'POSIUOH to the N=N Limited, Basel, Switzerland, a Swiss Company 5 g p and the group and 8 represents a No Drawing. Filed Nov. 30, 1965, Ser. No. 510,672 monocyclic benzene resldue. Claims priority, application Switzerland, Dec. 2, 1964, The residue R or R may be a benzene residue sub- 15,506/64 stituted by two sulphonic acid groups and which contains US Cl 96 99 G03c 1/10 6 Claims at most an alkyl group, for example, a methyl group as 10 a further substituent. The said residue may also be a naphthalene residue substituted by two sulphonic acid ABSTRACT OF THE DISCLOSURE groups and which does not contain further substituents.

R and R is a naphthalene or, preferably, a benzene Photographic materials for the silver dyestuff bleachresidue which is bound in 1,4-position to the -N=N mg process. These materials are characterized In that they d NH CO groups. When a naphthalene residue contain on a support a layer containing silver halide and is present it may be unsubstituted or may contain a sulat least one Yellow dyestuff of the formula phonic acid group advantageously in a fl-position of the six-membered ring not bound to the N=N group. When R or R is a benzene residue it may contam as substituents, for example, one or two alkyl groups or a hydroxyalkoxy group, an alkoxy group or an acylamino group, and no further substituents in addition to the two last-mentioned groups, or an alkyl group. All these substituents advantageously contain not more than four carbon atoms.

Accordingly, the layer dyestuffs may advantageously in which R and R each represents a benzene or a naphthalene radical containing at least one sulfonic acid group, R and R each represents a benzene or a naphthalene radical bound in 1,4-position to the N=N- group and the -NHOC group and R and R each represents a benzene radical. These yellow dyestuifs are fast to diffusion, stable during drying and storage and easy to correspond to one of the formulae bleach.

H038 X X :11 Hots N=N j -NH-0o-R,-N=N-Rtco-HN -N=N' 503B:

Y Y nnand (4) The present invention provides photographic materials in which R preferably represents a benzene residue, X for the silver dyestuff bleaching process, which materials represents a hydrogen atom or an alkyl, alkoxy or an contain on a support a layer containing at least one dyeacylamino group advantageously derived from a lowstulf of the formula molecular weight fatty acid, Y represents a hydrogen atom or an alkyl group and m and n each represents an l) R N=NR NH-OC-R integer not greater than 2.

N=N-R '-COHNR 'N=NR Of special interest are dyestuifs of the formula X X H033 N=N SIOlH N=N NH 0C@ CO HN N=N Y Y SOaH H038 in which R and R each represents a benzene or a naphin which X and Y have the meanings given above. thalene residue containing at least one sulphonic acid The trisazo dyestuffs of the Formula 1 can be prepared group, R and R each represents a benzene or a naphfrom aminoazo dyestuffs of the formula thalene residue bound in 1,4-position to the N=N group and the NHOC group and R and R each R1 N N R2 represents a monocyclic residue having 5 to 6 ring mem- 111 Whlch 1 and 2 have the meaIllIlgS glVeIl above, these bars. aminoazo dyestuffs being obtained by coupling a diazos i l dyestugs of h formula tized aminobenzene sulphonic acid or aminonaphthalene disulphonic acid with an aminobenzene or aminonaph- (2) R N=NR NHOCR thalene capable of coupling in para-position to the amino N=NR CO-HNR N=NR group. When an aminoazo dyestuff of the Formula 6 3 4 is reacted in a molecular ratio of 2:1 with a dihalide, the dyestuffs of the Formula 1 may be present in multipreferably the dichloride, of an azobenzeneor azothiolayer material containing on a support a red-sensitized phene-dicarboxylic acid of the formula layer dyed with a cyan dyestuif, a green-sensitized layer (7) dyed with a magenta dyestutf and, finally, a blue'sen- 5 sitized layer dyed with a dyestuif of the Formula 1.

symmetrical trisazo dyestulfs are obtained. The residues The d e tutfs of the Formula 1 are generally very R and R in the Formula 1 and the Formula 7 are monoresistant to difiusion in the usual kinds of layer. They cyclic and thus contain a single benzene ring without any display no tendency to change into an opalescent or dull further Tings Connected therewith, either p y y form in the gelatine layers during drying and storage, anellation. 10 and they are easily reduced to harmless and/or easily The following compounds may be mentioned as startwater-extractable decomposition products in the dyestufi ing materials from which the trisazo dyestufis can be bleaching bath, prepared in the manner indicated above: The following examples illustrate the invention. Unless Diazo components r otherwise stated, the parts and percentages are by weight. 1-aminobenzene-2,4-disulphonic acid, 10 EXAMPLE 1 1-aminobenzene-2,5-disulphonic acid, 12 milligrams of the dyestuff of the formula HO: S 0CH3 (8) 15 0-? O5H N=NQNH OC N=N CONO-M 803B 110:; 1-amino-4-methylbenzene-2,S-disulphonic acid, are dissolved at 70 C. in 2 cc. of distilled water. The 1-aminonaphthalene-3,6-disulphonic acid, solution is cooled to 40 C. and added to 3.5 cc. of a 6% 2-amino-naphthalene-4,8-disulphonic acid, aqueous gelatine at 40 C. 3.3 cubic centimetres of a Z-aminonaphthalene-3,6-disulphonic acid, gelatine silver bromide emulsion at a temperature of 40 Z-aminonaphthaJene-5,7-disulphonic acid, C. are then added. If necessary, 1 to 2 cc. of an aqueous Z-aminonaphthalene-6,8-disulphonic acid, solution of a dispersing agent, for example, saponin, and 2-aminonaphthalene-4,6,8-trisulphonic acid, a hardening agent, for example, dimethylolurea, are 2-arninonaphthalene-3,6,8-trisulphonic acid, added. The mixture so prepared is cast on a glass plate Z-aminonaphthalene-1,5,7-trisulphonic acid. measuring 13 cm. X 18 cm. and dried.

The film is exposed behind a step-Wedge and the silver Couplmg compcnems image is developed in a 1methylamino-4-hydroxybenzenesulphate hydroquinone developer and fixed. fi ig' or i i g g g or 3: The image dyestutf is then bleached out depending on g y l g or oxy s i E g 40 the amount of silver present, in a bath containing 30 to roxyel jgf i l g i 100 parts by volume of 32% hydrochloric acid, 40 to 120 me y enzene ace y a mo m parts of potassium bromide, 30 to parts of thiourea phenylurea, 1-ammobenzene-w-methanesulphonic ester, 1- d 0001 t 0 01 t f 2 3 h d h n amino-Z- or 3-ethoxy benzene, l-amino-Z- or 3-;8-hydroxyan 0 par 0 y mxyp 2 per 1,000 parts by volume. Subsequently, excess silver 18 ethoxybenzene, l-am1no-2-fi-hydroxy-S-methylbenzene, I- m d b th t 100 t f hl amino-2-methoxy-S-methylbenzene, 1- amino-2,5-dimethre Ove m a a con ammg par S 0 so mm c de 100 parts of copper sulphate crystals and 50 parts b 1- -2- th -5-m th 1b 1- on of by volume. Fixation is then carried out in the usual manacetlc 1'ammonaphthalene'S'Sulphomc acld' ner. A yellow image which is the inverse of the silver Dicarboxylic acids wedge is obtained which is bleached pure white at the 50 areas where the silver was present in the greatest density. AZobenzene-3,3'-dicarboxylic acid, A yellow image of this kind can also form part of multi- 4,4-dimethylazobenzene-3,3-dicarboxylic acid, colour photographic material; in this case, the amounts of 4,4-dichloroazobenzene-3,3'-dicarboxylic acid, gelatine are adapted to suit the required thickness of the azobenzene-4,4'dicarboxylic acid, layers. 2,2'-dimethylazobenzene-5,5'-dicarboxylic acid, The dyestuif of the Formula 8 may be prepared as 2,2-dimethoxyazobenzene-5,5-dicarboxylic acid, follows: 2,2'-dichlor0azobenzene-5,5'-dicarboxylic acid, 60.6 parts of Z-aminonaphthalene-l,8-disulphonic acid, 2,2-dimethylazobenzene-4,4-dicarboxylic acid, in the form of the sodium salt, are dissolved in 1,000 parts 3,3-dichloroazobenzene-4,4'-dicarboxylic acid, of water, the solution is cooled with ice to 0 C., and 4,4'-dichloroazobenzene-5,5'-dicarboxylic acid, diazotized in the usual manner with parts of 37% hy- 2,2'-aZothiophene-5,5'-dicarboxylic acid. drochloric acid and 14 parts of sodium nitrite. 30.5 parts of Z-methoxy-S-methyl-l-aminobenzene are dissolved at The dyestuifs of the Formulae 1 to 5 can be prepared 60 to C. in 300 parts of water and 30 parts of 37% by known methods. Coupling to form the aminomonoazo hydrochloric acid, the solution is cooled with ice to 5' dyestuffs is carried out in an acid medium. 5 C. and added to the solution of the diazo compound. The Amines diflicult to couple may be coupled in the form batch is stirred for 24 hours at a temperature of 8 to 15 of their w-methanesulphonic acids, with subsequent elim- C. to complete the coupling time and can be shortened by ination of the methanesulphonic acid group. The aminobuffering the mineral acid with sodium acetate. The acidic azo dyestuffs are advantageously reacted with the dicarsuspension of the monoazo dyestufi is heated to 65 C. boxylic acid halide containing azo groups in the presence 70 and is then filtered at 30 C. of an agent capable of binding acid. Like the dyestuffs 6 parts of the aminomonoazo dyestuffs so obtained are themselves, the photographic layers containing, in acdissolved in 150 parts of water and then 5.2 parts of socordance with the invention, at least one dyestuff of the dium borate are added to the solution at room tempera- Formula 1 may also be prepared by known methods and lure. 2 parts of azobenzene-4,4'-dicarboxylic acid dichloused for the production of colored images. In particular, ride are dissolved in 50 parts by volume of warm acetone,

and the solution so obtained is added all at once to the solution of the aminoazo dyestufi. The reaction mixture is stirred for 12 to 14 hours at room temperature and is then heated to 60 C. and kept at that temperature for one hour. The trisazo dyestufi so formed is precipitated by the addition of 300 parts by volume of ethanol and 100 parts by volume of 7 N potassium acetate and is then isolated by suction filtration. Purification is effected by dissolving the dyestuff in 200 parts of Water, precipitating it by the addition of 50 parts by volume of ethanol and 100 parts by volume of 7 N potassium acetate, and again isolating it by suction filtration. After drying, about 4 parts of dyestufi are obtained.

The azobenzene-4,4-dicarboxylic acid dichloride can be prepared in the following manner:

93 parts of zinc dust are added during minutes to a mixture of 100 parts of para-nitrobenzoic acid, 700 parts of water and 400 parts by volume of sodium hydroxide solution, during which process the temperature rises to C. The reaction mixture is heated from to C., which causes it to thicken, and then 500 parts of water are added. The batch is stirred for 12 hours at 90 C.

The reaction mixture is then discharged into 10,000 parts of hot water whereby the azobenzene dicarboxylic acid dissolves. After purification by filtration, 25 parts of sodium hypochlorite solution containing 13 to 14% of active chlorine are added to the filtrate. 320 parts by volume of glacial acetic acid are added and the dicarboxylic acid precipitates. After one hour the batch is suction filtered and the filter cake is washed with 500 parts of 1% acetic acid and with 500 parts of water. The residue is dried in vacuo and 74 parts of azobenzene-4,4'-dicarboxylic acid are obtained in the form of a pink powder.

54 parts of azobenzene-4,4' dicarboxylic acid, 200 parts of phosphorus pentachloride, 1,420 parts by volume of orthodichlorobenzene and 5 parts of di-methyl formamide are heated to 150 C. and kept at that temperature for 20 minutes. The batch is allowed to cool to 80 C. and about half the amount of dichlorobenzene is distilled off in vacuo. The batch is allowed to cool overnight and the azobenzene-4,4'-dicarboxylic acid dichloride precipitates in the form of red crystals. The batch is filtered and the residue is washed with benzene and dried in vacuo at 50 C. 43 parts of acid chloride melting at 157 to 159 C. are obtained.

Any one of the dyestuffs II to XIX obtainable from the components listed in the following table may be incorporated in a gelatine layer in the manner indicated instead of the dyestuff of the Formula 8. These dyestuffs can be prepared in a manner analogous to that used for the dyestulf of the Formula 8.

Absorptlon max., Dyestufi No. Diazo component Coupling component Condensation component 111;:

I (=Formu1a [8])-... HOiS O O H: 436

I 0100- N=N 00001 N H: H:

I S 09H II H0118 $011: 430

NH: NH:

I 010 C- N=N C O 01 HaC III H023 C H: 400

I ClOC- N=N- G001 NH; C -NH1 I HsC I 5 Cali IV HOaS 400 NH: 010 0- N=N-- C001 Ha I I SOSH V HOiS OCHaCHzOH 434 I 0100- N=N- 0 001 NH, QNH: I 11:40

I S OaH VI a? OCHzCHzOH 410 NH: NH:

010 C-ON-N-O-C 001 Absorp tion max Dyestufl No. Dlazo component Coupling component Condensation component in};

XVI H 035 400 l NH: Cl

ClO C N=N- --C Cl 0 Ha 0 I O1- S 03H XVII H035 OCHzCOOH 400 I 0100 N=N-C -COCI -NH, QNH: Etc

XVIII H 033 0 C H; 420

I ClOC-C -N=NOOOC1 NH= O-NH:

I H 035- H3O I S 0 H XIX HOQS OOHICHQOH 420 I l oc-C -N=N--o 001 NH: ONm

l HO S- HaC EXAMPLE 2 34: O-HN H0 HOaS (2) A colorless gelatine layer containing no silver halide.

(3) A green-sensitized silver bromide emulsion in gelatine containing the magenta dyestufi of the formula I O H SOaH (4) A yellow filter layer containing the dyestuif of the formula (5) A blue-sensitized silver bromide emulsion in gela- 70 tine containing the yellow dyestuif of the Formula 8.

The gelatine layers may contain additives, for example,

wetting agents, hardeners and stabilizers for the silver halide. The material is manufactured in a manner such of film, 0.5 gram of dyestuif and a quantity of silver bromide corresponding to 1 to 1.2 grams of silver.

The film so prepared is exposed to red, green and blue light beneath a coloured diapositive. The reproduction is then developed in the following manner:

(1) Developing for 6 minutes in a bath containing,

per litre, grams of anhydrous sodium sulphate, 0.2

50 gram of 1-phenyl-3-pyrazolidone, 6 grams of hydroquinone, 35 grams of anhydrous sodium carbonate, 4 grams of potassium bromide and 0.3 gram of benztriazole.

l SOsH H0 (2) Washing with water for 5 minutes.

(3) Fixing for 6 minutes in a solution of 200 grams of sodium thiosulphate crystals and 20 grams of potassium metabisulphite in 1 litre of water.

(4) Washing With water for 5 minutes.

(5) Dyestuii bleaching for 3 to 12 minutes with a solution containing, per litre of water, 50 to 80 grams of potassium bromide, 40 to 80 grams of thiourea, 35 to 80 grams of 30% sulphuric acid and, if desired, 0.01 gram of 2-amino-3-hydroxyphenazine.

(6) Washing with water for 10 minutes.

(7) Bleaching residual silver for 5 minutes with a solution containing grams of copper sulphate crystals, 80 grams of potassium bromide and 15 ml. of 30% hydrothat each layer (except (2)) contains, per square metre chloric acid per litre of water.

1 1 (8) Washing with water for 5 minutes. (9) Fixing for 5 minutes in the manner described under 3.

(l) Washing with water for minutes. A true, positive image to be viewed in incident light and from the group consisting of benzene and naphthalene bound in 1,4-position to the -N=N- group and the NHOC group and R represents a benzene radical.

3. Photographic material as claimed in claim 1 in which the layer contains silver halide and a dyestuff of which is fast to light and otherwise permanent is obtained. 5 the formula HOaS HOS

in which R represents a radical selected from the group 15 consisting of benzene and thiophene, X represents a member selected from the group consisting of a hydrogen atom, an alkyl group, and an alkoxy group, Y represents a member selected from the group consisting of a hydrogen atom and an alkyl group, and m and 11 each represents an integer of at the most 2.

4. Photographic material as claimed in claim 1, in which the layer contains silver halide and a dyestulf of the formula in which R and R each represents a radical selected in which R represents a benzene radical, X represents from the group consisting of benzene and naphthalene containing at least one sulphonic acid group, R and R each represents a radical selected from the group consisting of benzene and naphthalene bound in 1,4-position to the N N group and the NHOC group and R and R each represents a benzene radical.

2. Photographic materials as claimed in claim 1, where- HOaS SOzH

a member selected from the group consisting of a hydrogen atom, an alkyl group, and an alkoxy group and Y represents a member selected from the group consisting of a hydrogen atom and an alkyl group.

5. Photographic material as claimed in claim 4, in which the layer contains silver halide and a dyestuff of the formula SOaH HOrS

in the layer contains silver halide and a dyestufi of in which X represents a member selected from the group the formula in which R represents a radical selected from the group consisting of benzene and naphthalene containing at least two sulfonic acid groups, R represents a radical selected Hots oona HaC-O S 0311 References Cited UNITED STATES PATENTS 6/1942 Chechak 96-99 I. TRAVIS BROWN, Primary Examiner.

US. Cl. X.R. 

